Method for preparing laminated precursor rolls

ABSTRACT

Laminate precursors are prepared by applying an aqueous foamed opacifying composition to a non-woven fabric, drying, optionally applying an anti-blocking material to the dried aqueous foamed opacifying composition, and densifying the dry foamed opacifying layer so that it will have a thickness that is at least 20% less than its thickness before densifying. Each laminate precursor is rolled up for immediate or later use to make laminate decorative articles when the unrolled laminate precursor is laminated with back side of a decorative fabric. The applied aqueous foamed opacifying composition has 35%-70% solids and a foam density of 0.1-0.5 g/cm3. It is composed of (a) porous particles, (b) a binder material, (c) two or more additives comprising at least one foaming surfactant and at least one foam stabilizer, (d) an aqueous medium, and (e) an opacifying colorant that absorbs electromagnetic radiation having a wavelength of 380-800 nm.

RELATED APPLICATIONS

Reference is made to the following related applications:

U.S. Pat. No. 10,942,300, issued Mar. 9, 2021, by Nair and Brick;

U.S. Pat. No. 11,275,203, issued Mar. 15, 2022, by Nair and Brick;

U.S. Pat. No. 11,549,213, issued Jan. 10, 2023; and

U.S. Pat. No. 11,181,247, issued Nov. 23, 2021

the disclosures of all of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to the field of light-blocking materials. Inparticular, this invention relates to a method for making laminatedlight-blocking decorative articles having opacifying or light-blockingeffect, which articles can be used to form decorative drapes, shades,blinds, or other light-blocking materials. Such laminated light-blockingdecorative articles can be prepared by preparing multiple rolls ofcoated non-woven fabrics, and any of the rolls can then be unrolled andlaminated to a chosen decorative fabric. This invention also relates tolaminate precursor rolls that can be used at any time to make laminatedlight-blocking decorative articles.

BACKGROUND OF THE INVENTION

In general, when light strikes a surface, some of it may be reflected,some absorbed, some scattered, and the rest transmitted. Reflection canbe diffuse such as light reflecting off a rough surface like a whitewall, in all directions, or specular, as in light reflecting off amirror at a definite angle. A 100% opaque substance transmits almost nolight, and therefore reflects, scatters, or absorbs all of it. Bothmirrors and carbon black are opaque. Opacity depends on the selectiveabsorption of the frequency of the light being considered. “Blackout” orlight blocking materials typically refer to coated layers in articlesthat are substantially impermeable to light such as visible and UVradiation. Thus, when a blackout material such as a blackout curtain orblackout shade is hung over a window, it generally blocks substantiallyall external light from entering the room through that window. Blackoutmaterials are suitable as curtains or shades for use in homes, forinstitutional use in hospitals, nursing homes, and offices as well asfor use in commercial establishments such as hotels, theaters, andaircraft windows where the option of excluding light can be desirable.

Light blocking articles such as the blackout curtains can be comprisedof a fabric (porous substrate) coated with several layers of alight-blocking composition. There is a need for these curtains, inaddition to blocking transmitted light, to have a light color (hue)facing the environment to aid in illumination to minimize the amount ofartificial lighting needed to perform the activity. An example is whenthe function of the blackout material is to separate two areas ofactivity where one or both areas can be artificially lit at the sametime. More often than not, the function of a blackout curtain is toprevent sunlight from entering a room through a window. It can also bedesirable for the color (hue) of the side facing the window to match theexterior decor of the building.

Light colored blackout coatings theoretically can be made by coatingporous fabrics with light colored foams containing light scatteringpigments such as titanium dioxide or clays. However, when using onlythese pigments, very thick foam coatings will be needed to createblackout curtains through which the sun is not visible in a darkenedroom. One method that is practiced for reducing the weight of suchblackout materials is to sandwich a light-absorbing, foamed black orgrey pigment, such as a carbon black between two foamed lightscattering, white pigment-containing layers.

When an electromagnetic radiation blocking coating has, as it oftendoes, a strongly light absorbing material containing black pigments suchas carbon black, between two reflective layers, it has at least twodistinct problems. First, such materials require three or more separatecoating operations that reduce manufacturing productivity and increaseunit costs. Secondly, carbon black in the light absorbing middle layercan become “fugitive” during sewing or handling as a result of apuncture or tear, and soil or discolor other layers such as thereflective layers, which is highly objectionable. Additionally, thestitches generated in the materials during sewing can cause the fugitivecarbon black from the light absorbing layer to spread over a larger areathereby increasing the area of objectionable contamination of thelight-colored surface.

U.S. Pat. No. 9,891,350 (Lofftus et al.) describes improved articlesthat are designed with an opacifying layer applied to a substrate andthat are capable of blocking predetermined electromagnetic radiation.

An improvement in this art is described in U.S. Pat. No. 9,469,738 (Nairet al.) in which small amounts of porous particles containing smallamounts of opacifying colorants can be incorporated into foamedcompositions that have a foam density of at least 0.1 g/cm³. Such foamedcompositions can be applied to a substrate to provide opacification.U.S. Pat. No. 9,963,569 (Nair et al) describes similar technology formaking opacifying element using a foamed aqueous latex composition.

U.S. Pat. No. 6,884,491 (Rubin et al.) describes water repellant, waterresistant, and stain resistant fabrics that are prepared using treatedtextile fabrics that are laminated to a backing polymeric film.

It is known to make decorative articles such as draperies using backingliners formed from woven or non-woven fabrics. A typical drapery can bea rectangular piece of decorative fabric whose edges are folded back andhemmed. A drapery made from a single layer of decorative textile fabricis less expensive than a lined drapery but it suffers from thedifficulty that it is not fully opaque and that sunlight transmissioncan cause fading of dyes in the drapery as well in other articles orprevent desired darkening in a room which the drapery is hung. A lineddrapery is generally constructed from a relatively high qualitydecorative fabric that can be printed, embossed, or otherwise carries adesign, together with a lining that can be formed from a suitable lessexpensive woven or non-woven fabric. Such lining functions to reduce thetransmission of light to impact the expensive decorative fabric. Thelining can also add opacity to make it more difficult for outsiders tosee into a room, and it may also provide insulative properties bytrapping air between it and the decorative fabric. In addition, a liningcan also add some weight to a drapery so that it hangs better. However,lined draperies are more expensive not just because of additionalmaterial but because of fabrication costs to attach the lining to thedecorative fabric.

A number of solutions have been proposed in the industry to reduce thecosts and to achieve the advantages of linings, including the use offoamed linings or foamed adhesives between decorative fabrics andlinings. A composite lining comprises a typical inexpensive woven ornon-woven material useful as a backing material and a foamed organicpolymer that functions as an adhesive for a decorative textile fabric,as described for example, in U.S. Pat. No. 3,748,217 (May et al.). Thefoamed organic polymer can be applied to a decorative fabric before theinexpensive woven or non-woven or material is laminated to thedecorative textile fabric-adhesive combination, followed by curing.

Decorative blackout draperies are described in U.S. Pat. No. 5,741,582(Lederman et al.) in which an opaque adhesive is applied to a textilematerial (first substrate) and a second material (second substrate) isthen adhered thereto to provide a decorative drapery surface on one sideand a lining on the opposing side of the opaque adhesive. The opposingmaterials can be formed from any suitable woven or non-woven textilecomposed of naturally-occurring or man-made fibers. The opaque adhesivecan be provided as an acrylic foam containing a black or dark pigment,which acrylic foam is eventually crushed and cured once coated. Multipleadhesive layers can be used if desired, as applied to opposing first andsecond substrates. Unfortunately, the black or dark pigment in theopaque adhesive layer can show through both textiles that sandwich itand add discoloration to the fabric, unless outer layers of white foamare coated on either side of the black foam to hide that layer andminimize both coloration and fugitive black pigments such as carbonblack. This becomes an expensive process that could compromise thedecorative fabric during the coating processes.

Decorative fabrics can also be prepared by providing opacifyingcompositions on their backside and then applying a flock to theopacifying composition for feel and appearance. However, many convertorsare not happy with the use of flock because it can dust off the articleduring various down-stream treatments and become a product contaminantand an environmental health hazard for its flammability and humaninhalation of particulate fibers. Moreover, it is hard to apply flock ina uniform manner unless it is applied using electrostatic means andapparatus, which is a very expensive operation. Thus, there is a need toavoid the use of flock if possible.

There is also a need for an improved and inexpensive means to provide avariety of laminated light-blocking decorative articles in which flockis avoided but desired fabric feel is achieved on the surface oflight-blocking coatings. Moreover, there is a need to make low volumesof laminated light-blocking decorative articles to provide convenienton-demand manufacturing without having to coat short runs.

SUMMARY OF THE INVENTION

The present invention provides a method comprising, in order:

A) independently providing one or more different non-woven fabrics, eachnon-woven fabric having a face side and a back side;

B) applying an aqueous foamed opacifying composition to the back side ofthe one or more different non-woven fabrics, the wet coverage of theapplied aqueous foamed opacifying composition being the same ordifferent on each of the one or more different non-woven fabrics;

C) drying each applied aqueous foamed opacifying composition to providea dry coverage of less than or equal to 1000 g/m² of a dry foamedopacifying layer having a light blocking value (LBV_(oc)) of at least 2;

D) optionally, either between the B) applying step and the C) dryingstep, or immediately after the C) drying step, applying an anti-blockingmaterial to each applied aqueous foamed opacifying composition to formone or more laminate precursors having an anti-blocking material backside and a non-woven fabric face side, the one or more laminateprecursors comprising one or more different non-woven fabrics on itsface side and the same or different dry coverage of applied aqueousfoamed opacifying composition on the anti-blocking material back side;

E) simultaneously with or subsequent to the optional D) applying step,densifying the dry foamed opacifying layer so that it will have athickness that is at least 20% less than its thickness beforedensifying;

F) rolling up each of the one or more laminate precursors, to provideone or more laminate precursor rolls,

-   -   wherein the aqueous foamed opacifying composition has at least        35% and up to and including 70% solids and a foam density of at        least 0.1 g/cm³ and up to and including 0.5 g/cm³, and        comprises:    -   (a) porous particles in an amount of at least 0.05 weight % and        up to and including 20 weight %, each porous particle comprising        a continuous polymeric phase and discrete pores dispersed within        the continuous polymeric phase, the porous particles having a        mode particle size of at least 2 μm and up to and including 50        μm and a porosity of at least 20 volume % and up to and        including 70 volume %;    -   (b) a binder material in an amount of at least 15 weight % and        up to and including 70 weight %,    -   (c) two or more additives in an amount of at least 0.0001 weight        % and up to and including 30 weight %, the two or more additives        comprising at least one foaming surfactant and at least one foam        stabilizer,    -   (d) an aqueous medium, and    -   (e) an opacifying colorant in an amount of at least 0.0001        weight % and up to and including 0.5 weight %, which opacifying        colorant being different materials from the (a) porous        particles, (b) binder material, and (c) two or more additives,        and which opacifying colorant absorbs electromagnetic radiation        having a wavelength of at least 380 nm and up to and including        800 nm,    -   all amounts of (a) porous particles, (b) binder material, (c)        two or more additives, and (e) opacifying colorant being based        on the total weight of the aqueous foamed opacifying        composition.

In some embodiments, the D) applying step is carried out, so that whenthe one or more laminate precursors are rolled up, the anti-blockingmaterial back side is in contact with the face side of a non-wovenfabric.

In addition, the method can further comprise:

G) providing a decorative fabric having a face side and a back side; and

H) unrolling a laminate precursor roll from the one or more laminaterolls and laminating the back side of the decorative fabric to the dryfoamed opacifying layer of the unrolled laminate precursor roll,

to form a laminated light-blocking decorative article.

Alternatively, the method can further comprise:

G) providing a decorative fabric having a face side and a back side; and

H) unrolling a laminate precursor roll from the one or more laminaterolls and laminating the back side of the decorative fabric to theanti-blocking material back side of the unrolled laminate precursorroll,

-   -   to form a laminated light-blocking decorative article.    -   The present invention also provides a laminate precursor roll        comprising a non-woven fabric having a face side and a back        side, a dry foamed opacifying layer that is disposed on the back        side of the non-woven fabric, and a non-blocking composition        disposed on the dry foamed opacifying layer,

wherein the face side of the non-woven fabric is rolled up in contactwith the non-blocking composition, and

the dry foamed opacifying layer being present at a dry coverage of lessthan or equal to 1000 g/m², and comprising:

-   -   (a) porous particles in an amount of at least 0.1 weight % and        up to and including 35 weight %, each porous particle comprising        a continuous polymeric phase and discrete pores dispersed within        the continuous polymeric phase, the porous particles having a        mode particle size of at least 2 μm and up to and including 50        μm and a porosity of at least 20 volume % and up to and        including 70 volume %;    -   (b′) a matrix material that is derived from a (b) binder        material having a glass transition temperature (T_(g)) of less        than 25° C., which (b′) matrix material is present in an amount        of at least 10 weight % and up to and including 80 weight %,    -   (c) two or more additives in an amount of at least 0.0001 weight        % and up to and including 50 weight %, the two or more additives        comprising at least one foaming surfactant and at least one foam        stabilizer,    -   (d) an aqueous medium in an amount of less than 5 weight %, and    -   (e) an opacifying colorant in an amount of at least 0.002 weight        % and up to and including 2 weight %, which opacifying colorant        being a different material from the (a) porous particles, (b′)        matrix material, and (c) two or more additives, and which        opacifying colorant absorbs electromagnetic radiation having a        wavelength of at least 380 nm and up to and including 800 nm,    -   all amounts of (a) porous particles, (b′) matrix material, (c)        two or more additives, (d) aqueous medium, and (e) opacifying        colorant being based on the total weight of the dry foamed        opacifying layer.

The present invention provides a method whereby various rolls oflaminate precursors having opacifying coatings can be prepared and usedas needed (“on-demand”) for lamination to decorative fabrics without theneed for coating a polymer latex foam directly on the decorative fabric,or for using a metallized layer or flock. Such laminate precursors canbe provided for manufacturing short- or long-run batches of laminatedlight-blocking decorative articles (such as blackout draperies) havingcustomized features as provided by the non-woven fabrics, therebyminimizing waste of directly-coated decorative fabrics. For example,where test samples of blackout (light-blocking) articles derived fromdecorative fabrics are needed by designers to mock up a room, on-demandlamination of various laminate precursors from individual rolls at arequired yardage of the decorative fabrics becomes more economical thansubmitting excess decorative fabric to a coating conversion that may notsuit the decor until after the fact. In a sense, the present inventionprovides a means for “proofing” a customer's expectations without usingdirectly coated decorative fabrics. The present invention alsoeliminates the need for sewing an extra blackout liner and attaching thesame to a decorative fabric and avoids the unsuitable multi-blackoutcompositions, linings, and sandwiched layers commonly used in theindustry.

The non-woven fabrics used in this invention can be customized to havevarious features including printed images and colors.

Moreover, while flock and its problems are avoided, the resultinglaminated light-blocking decorative articles are soft to the touch, andcan be designed with any desired weight, stiffness (for example, forused as roller shades), or coloration while sufficiently blocking outimpinging light. Decorative fabrics used in the manufacturing operationare spared from the risk and expense of stressful coating operations andmultiple passes with stretching or tentering.

DETAILED DESCRIPTION OF THE INVENTION

The following discussion is directed to various embodiments of thepresent invention and while some embodiments can be desirable forspecific uses, the disclosed embodiments should not be interpreted orotherwise considered to limit the scope of the present invention, asclaimed below. In addition, one skilled in the art will understand thatthe following disclosure can have broader use than is explicitlydescribed or discussed for any particular embodiment.

Definitions

As used herein to define various components of the aqueous foamedopacifying composition and dry foamed opacifying layer, that is the (a)porous particles, (b) binder materials, (c) two or more additives, (e)opacifying colorant, and other materials used in the practice of thisinvention, and unless otherwise indicated, the singular forms “a,” “an,”and “the” are intended to include one or more of the components (thatis, including plurality referents).

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the term shouldbe interpreted as having a standard dictionary meaning.

The use of numerical values in the various ranges specified herein,unless otherwise expressly indicated otherwise, are to be considered asapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges may be useful toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values aswell as the end points of the ranges.

Unless otherwise indicated, the terms “dry foamed opacifying layer” and“dry foamed opacifying layer” are intended to refer to the same feature.

The terms “porous particle” and “porous particles” are used herein,unless otherwise indicated, to refer to porous bead-like polymericmaterials useful in the aqueous foamed opacifying compositions essentialfor the present invention. As defined in detail below, the porousparticles generally comprise a solid continuous polymeric phase havingan external particle surface and discrete pores dispersed within thecontinuous polymeric phase. The continuous polymeric phase also can bechemically crosslinked or elastomeric in nature.

The continuous polymeric phase of the porous particles generally has thesame composition throughout that solid phase. That is, the continuouspolymeric phase is generally uniform in composition including anycomponents [for example, (e) opacifying colorant] that can beincorporated therein. In addition, if mixtures of polymers compose thecontinuous polymeric phase, generally those mixtures also are uniformlydistributed throughout.

As used in this disclosure, the term “isolated from each other” refersto the different (distinct) pores of the same or different sizes thatare separated from each other by some portion of the continuous solidphase and such discrete pores are not interconnected. Thus, “discrete”pores refer to “individual” or “closed” non-connected pores or voidsdistributed within the continuous polymeric phase.

The (a) porous particles can include “micro,” “meso,” and “macro”discrete pores, which according to the International Union of Pure andApplied Chemistry, are the classifications recommended for discrete poresizes of less than 2 nm, from 2 nm to and including 50 nm, and greaterthan 50 nm, respectively. Thus, while the (a) porous particles caninclude closed discrete pores of all sizes and shapes (that is, closed,non-interconnected discrete pores entirely within the continuouspolymeric phase) providing a suitable volume in each discrete pore,macro discrete pores are particularly useful. While there can be openmacro pores on the surface of the (a) porous particle, such open poresare not desirable for providing the advantages of the present invention,and may be present only by accident. The size of the (a) porousparticles, their formulation, and manufacturing conditions are theprimary controlling factors for discrete pore size. However, typicallythe discrete pores have an average size of at least 0.1 nm and up to andincluding 7,000 nm, or more likely at least 200 nm and up to andincluding 2,000 nm. Whatever the size of the discrete pores, they aregenerally distributed randomly throughout the continuous polymericphase. However, if desired, the discrete pores can be groupedpredominantly in one part (for example, in a “core” portion or in a“shell” portion) of the (a) porous particles.

Unless otherwise indicated, the term “non-porous” refers to particlesthat are not designed to have discrete pores or compartments within thesolid continuous polymeric phase and less than 20% of their total volumeconsists of pores.

“Opacity” is a measured parameter of an opacifying element according tothe present invention, which characterizes the extent to which thetransmission of electromagnetic radiation such as visible light isblocked. A greater opacity indicates a more efficient blocking (hiding)of electromagnetic radiation or high light-blocking for the dry foamedopacifying layer.

Glass transition temperature of the organic polymers used to prepare thecontinuous polymeric phase, or (b) binder materials described below, canbe measured using Differential Scanning Calorimetry (DSC) using knownprocedures. For many commercially available organic materials, the glasstransition temperatures are known from suppliers.

The terms “decorative fabric” and “non-woven fabric” are defined below.

The term “fabric” is meant to refer to a material composed of orprepared from naturally occurring fibers, synthetic fibers, or a mixtureof naturally occurring fibers and synthetic fibers of any desirablelength.

Uses

The method according to this invention can provide a means for easilymaking one or more rolls of laminate precursors that can be used asneeded to provide laminated light-blocking decorative articles ofdesired weight, stiffness, opacity, color, and feel. These laminatedlight-blocking decorative articles can have suitable light-blockingproperties and color for use in various environments and structures.Such laminated light-blocking decorative articles may also exhibitimproved sound and heat blocking properties. They can be used as, forexample, draperies and other window treatments, room dividers, cubiclecurtains, banners, labels, coverings and tarpaulins (for example forvehicles, boats, and other objects), and packaging materials. Thelaminated light-blocking decorative articles can optionally have one ormore printable outer surfaces that are able to accept ink used in screenprinting, gravure printing, inkjet printing, thermal imaging (such as“dye sublimation thermal transfer”), or other imaging processes. Asdecorative surfaces go, the laminate precursor rolls and laminatedlight-blocking decorative articles prepared according to the presentinvention can have any type of decorative image, text, pattern, orcombination thereof, as can be conceivably created by a person ormachine.

For example, laminate light-blocking decorative articles can be windowshades having blackout properties, feel, and other properties desired bythe customer.

Non-Woven Fabrics

Each non-woven fabric used in the practice of the present invention hastwo opposing sides, that is a face side and a back side. These twoopposing sides can be the same or different in appearance, texture,feel, antimicrobial properties, or chemical composition, but the backside and face side labels are used to distinguish how the opacifyingelement is arranged in relation to the applied aqueous foamed opacifyingcomposition (and optional anti-blocking material) and decorative fabricas described in the text below.

For example, the non-woven fabric can be composed of a blended ornonblended fabric, and can be considered as spunlaced non-woven fabrics(or tanglefaced non-woven fabrics). Spunlaced non-woven fabrics aregenerally textile fabrics consisting of fibers entangled in apredetermined pattern to form a strong, unbonded structure. Thus, suchnon-woven fabrics can be typically in the form of fabrics composed offibers locked into place by fiber interaction, thereby providing acohesive structure without the need for chemical binders or fiberfusing.

Useful non-woven fabrics can be formed from naturally-occurring fibers,synthetic fibers, or mixtures of naturally-occurring fibers andsynthetic fibers. Alternatively, an outer surface can be covered bysuitable means with a colorless continuous or discontinuous layer toprovide a desired protective finish, or anti-microbial or soil releaseproperties. In many instances, the image formed in this manner, forexample, on an outer surface, is not visible or discernible from theother outer surface of the laminated decorative article. Polyesterfibers are particularly useful, especially for spunlaced non-wovenfabrics. In additions, blends of one or more naturally-occurring fibersand synthetic fibers can be used.

It is also possible that the non-woven fabrics are suitably tinted orcolored using dyes or pigments that would be readily apparent to oneskilled in this art in the fabric industry. Moreover, the non-wovenfabrics can have one or more printed pattern or images on the face side,and such patterns or images can be provided before or after laminationto the decorative fabric.

Useful non-woven fabrics can be obtained from various industrialsources, and the processes for making them are well known including theteachings in U.S. Pat. No. 3,748,217 (noted above), the disclosure ofwhich is incorporated herein by reference, especially with respect tothe teaching in Cols. 3 and 4 and the references cited therein.

Useful non-woven fabrics can have a basis weight (or “fabric weight”) ofat least 0.5 oz/yd² (or 16.95 g/m²), or at least 1 oz/yd (33.9 g/m²). Inother embodiments, the basis weight for non-woven fabrics used in thisinvention can up to and including 25 oz/yd² (or 847.7 g/m²), or up toand including 12.5 oz/yd² (423.9 g/m²).

Thus, in the practice of this invention, the various non-woven fabricsused to provide the various rolls of laminate precursors can have thesame or different color, stiffness, textile, feel, chemical composition,or other mechanical or chemical properties. This is one of the mainadvantages of the present invention in that the various non-wovenfabrics can be different in any desired manner.

In many embodiments, the non-woven fabric can comprise a material thathas been treated in one or more ways to provide water-repellency orstain resistance, or both, particularly on its face side. For example,such treatments can comprise applying a suitable fluorochemical treatingagent, with or without a suitable antimicrobial agent (or biocide), toeither or both of the face and back sides of a non-woven fabric materialas well as to interstitial spaces within the non-woven fabric material,to provide a “treated” non-woven fabric, followed by suitable drying orcuring at elevated temperatures. A representative treatment process isdescribed in Cols. 4-6 of U.S. Pat. No. 6,884,491 (noted above) as wellin Cols. 6ff of U.S. Pat. No. 6,541,138 (Bullock et al.), thedisclosures of both of which are incorporated herein by reference. Thetreatment solutions can include one or more biocides (such asantimicrobials), crosslinking agents (including self-crosslinking latexpolymers), soil releasing agents, fire retardants, smoke suppressants,dispersants, thickeners, dyes, pigments, UV light stabilizers, and otheradditives that would be readily apparent to one skilled in the art. Suchtreatments can be particularly useful on the face side of the non-wovenfabric.

In general, suitable non-woven fabrics can have a dry average thicknessof at least 50 μm, and the thickness can depend upon various industrialand customer factors. This dry average thickness can be determined whenthe non-woven fabric comprises less than 5 weight % water (based on thetotal weight of the non-woven fabric) using the average of at least 3measurements taken at different places, or as determined using asuitable micrograph image.

Decorative Fabrics

Each decorative fabric used according to the present invention has twoopposing sides, that is a face side (usually a viewable or observer'sside) and a back side. These two opposing sides can be the same ordifferent in appearance, texture, feel, pattern, color, or composition,but the back side and face side labels are used to distinguish how thedecorative fabric is arranged in relation to the unrolled laminateprecursor. The face side of such decorative fabrics can be any desiredimage, raised texture, “quilting”, or embossed design, and thusgenerally have a decorative function. Means for providing thisdecorative function are known in the art and include but are not limitedto, decorative weaving, printing using dye sublimation, screen ordigital printing, and inkjet printing. Thus, decorative fabrics aregenerally fabrics having decorative applied art and can be patterned,embossed, or printed. The ornamentation of such decorative fabrics canconsist of repeated patterns and is achieved either by weaving,printing, or embroidering. For example, the decorative fabric can be awoven fabric having a repeating design pattern that is woven orembroidered into the decorative fabric.

A decorative fabric can be in the form of woven or non-woven materialsthat are composed of naturally-occurring fibers, synthetic fibers, ormixtures of naturally-occurring fibers and synthetic fibers. Suitablenaturally-occurring fibers include but are not limited to, fibers ofcotton, linen, ramie, silk, wool, and others known in the natural world,and blends of fibers of such naturally-occurring materials. Suitablesynthetic fibers include but are not limited to, fibers of nylon,polyesters, acrylics, glass (fiberglass), polyurethanes, polyamides,polycarbonates, rayon, polyolefins, celluloses (include woven ornon-woven paper materials), acetates, aromatic polyamides, polyvinylchloride, and others known in the art, as well as combinations or blendsof any of these types of fibers, such as polyvinyl chloride coatedfibers of various materials. Useful fabrics also can be composed ofpolyvinyl chloride-clad polyester or polyvinyl chloride-clad fiberglass.Suitable fabric materials include but are not limited to, double clothjacquards (that is fabrics manufactured on a jacquard loom), brocades,dobby fabrics, prints, poplins, cross-dyes, crepes, and canvasses.

In some embodiments, the decorative fabric is a porous fabric comprisinga plurality of continuous yarn strands, all woven together, wherein eachyarn strand comprises a multifilament core that is coated with a coatingcomprising a thermoplastic polymer. Further details for such decorativefabrics and their use are provided in U.S. Patent ApplicationPublication 2018/0223474 (Nair et al.), the disclosure of which isincorporated herein by reference.

In many embodiments, the decorative fabric can comprise a material thathas been treated in one or more ways to provide water-repellency orstain resistance, or both, on either or both face and back sides. Forexample, such treatments can comprise applying a suitable fluorochemicaltreating agent, with or without a suitable antimicrobial agent (orbiocide), to the face side and back side of a decorative fabric materialas well as to interstitial spaces within the decorative fabric material,to provide a “treated” decorative fabric, followed by suitable drying orcuring at elevated temperatures. A representative treatment process isdescribed in Cols. 4-6 of U.S. Pat. No. 6,884,491 (noted above) as wellin Cols. 6ff of U.S. Pat. No. 6,541,138 (Bullock et al.), thedisclosures of both of which are incorporated herein by reference. Thetreatment solutions can include one or more biocides (such asantimicrobials), crosslinking agents (including self-crosslinking latexpolymers), soil releasing agents, fire retardants, smoke suppressants,dispersants, thickeners, dyes, pigments, UV light stabilizers, and otheradditives that would be readily apparent to one skilled in the art.

For example, a decorative fabric material can be treated with at leastone or more biocidal agents capable of destroying or preventing theactivity of bacteria, viruses, fungi, or mold, many of which materialsare known in the art, including antibiotics, trialkyl tin compounds,copper compounds, copper complexes of dehydroabietyl amine or8-hydroxyquinolinium 2-ethylhexoate, copper naphthenate, copper oleate,organosilicon quaternary ammonium compounds, silver metal and varioussilver salts.

One or more treatments of the decorative fabric material can be carriedout to achieve the desired properties while maintaining desired hand,feel, texture, drape, and aesthetic appearance.

In general, suitable decorative fabrics can have a dry average thicknessof at least 50 μm, and the thickness can depend upon the use of thelaminated decorative article and the type of decorative fabric materialsavailable for use. This dry average thickness can be determined when thedecorative fabric comprises less than 5 weight % water (based on thetotal weight of the decorative fabric) using the average of at least 3measurements taken at different places, or as determined using asuitable micrograph image.

The decorative fabric can also have an openness of at least 0% and up toand including 10%, or even at least 1% and up to and including 10%.“Openness” (Openness Factor, or OF) refers to how tight the weave is ina decorative fabric material, the percentage of holes in a fabricconstruction, and is sometimes referred to as “weave density.” The lowerthe OF, the less the light transmittance and the greater the visiblelight that is obstructed or blocked. It is the ratio between transparentand opaque surfaces and depends on the spacing and dimension of theyarn.

Aqueous Foamed Opacifying Compositions

Each aqueous foamed opacifying composition comprises five essentialcomponents (a), (b), (c), (d), and (e) as defined below that areessential for providing desired properties in a dry foamed opacifyinglayer produced by the method of this invention.

The aqueous foamed opacifying composition generally has at least 35%solids and up to and including 70% solids, or more particularly at least40% solids and up to and including 60% solids.

(a) Porous Particles:

Porous particles used in the present invention containing discrete pores(or compartments or voids) are generally prepared using one or morewater-in-oil emulsions in combination with an aqueous suspensionprocess, such as in the Evaporative Limited Coalescence (ELC) processthat is known in the art. The details for the preparation of the porousparticles are provided, for example, in U.S. Pat. Nos. 8,110,628 (Nairet al.), 8,703,834 (Nair), 7,754,409 (Nair et al.), 7,887,984 (Nair etal.), 8,329,783 (Nair et al.), and 8,252,414 (Putnam et al.), thedisclosures of all of which are incorporated herein by reference. Thus,the porous particles can be made by a multiple emulsion process thatprovides formation of individual porous particles comprising acontinuous polymer phase and multiple discrete internal pores, and suchindividual porous particle is dispersed in an external aqueous phase.The described Evaporative Limited Coalescence (ELC) process is used tocontrol the particle size and distribution while a hydrocolloid isincorporated to stabilize the inner emulsion of the multiple emulsionsthat provide the template for generating the discrete pores in theporous particles.

The (a) porous particles used in this invention generally have aporosity of at least 20 volume %, at least 35 volume %, or at least 40volume %, and up to and including 60 volume %, up to and including 65volume %, or up to and including 70 volume %, all based on the totalporous particle volume. Porosity can be measured by an obviousmodification of the known mercury intrusion technique. Except as notedbelow, the volume of each discrete pore is essentially full of air withperhaps some non-evaporated water present.

Thus, the (a) porous particles are generally polymeric and organic innature (that is, the continuous polymeric phase is polymeric and organicin nature) and non-porous particles (having less than 20% porosity) areexcluded from use in the present invention. Inorganic particles can bepresent on the outer surface of each porous particle if desired.

The (a) porous particles can be composed of a continuous polymeric phasederived from one or more organic polymers that are chosen so that thecontinuous polymeric phase has a glass transition temperature (T_(g)) ofat least 25° C., or more typically of at least 25° C. and up to andincluding 180° C., as determined using Differential ScanningCalorimetry.

The continuous polymeric phase can comprise one or more organic polymershaving the properties noted above, in an amount of at least 70 weight %and up to and including 100 weight % based on the total polymer weightin the continuous polymeric phase. In some embodiments, the continuouspolymeric phase is composed of one or more cellulose polymers (orcellulosic polymers) including but not limited to, those cellulosicpolymers derived from one or more of cellulose acetate, cellulosebutyrate, cellulose acetate butyrate, and cellulose acetate propionate.Mixtures of these cellulose polymers can also be used if desired, andmixtures comprising a polymer derived from cellulose acetate butyrate asat least 80 weight % of the total of cellulose polymers (or of allpolymers in the continuous polymeric phase) are particularly usefulmixtures. Details about such polymers are provided, for example, in U.S.Pat. No. 9,963,569 (Nair et al.), the disclosure of which isincorporated herein by reference.

In other embodiments, the continuous polymeric phase can comprise one ormore organic polymers such as polyesters, styrenic polymers (for examplepolystyrene and polychlorostyrene), mono-olefin polymers (for example,polymers formed from one or more of ethylene, propylene, butylene, andisoprene), vinyl ester polymers (for example, polymer formed from one ormore of vinyl acetate, vinyl propionate, vinyl benzoate, and vinylbutyrate), polymers formed from one or more a-methylene aliphaticmonocarboxylic acid esters (for example, polymers formed from one ormore of methyl acrylate, ethyl acrylate, butyl acrylate, dodecylacrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethylmethacrylate, butyl methacrylate, and dodecyl methacrylate), vinyl etherpolymers (such as polymers formed from one or more of vinyl methylether, vinyl ethyl ether, and vinyl butyl ether), and vinyl ketonepolymers (for example, polymers formed from one or more of vinyl methylketone, vinyl hexyl ketone, and vinyl isopropenyl ketone). Other usefulpolymers include polyurethanes, urethane acrylic copolymers, epoxyresins, silicone resins, polyamide resins, and polyesters of aromatic oraliphatic polycarboxylic acids with one or more aliphatic diols, such aspolyesters of isophthalic or terephthalic or fumaric acid with diolssuch as ethylene glycol, cyclohexane dimethanol, and bisphenol adductsof ethylene or propylene oxides. The polyesters can be saturated orunsaturated. Other useful polyesters include lactic acid polymers,glycolic acid polymers, caprolactone polymers, and hydroxybutyric acidpolymers. Details of such useful polymers are provided, for example inU.S. Pat. Nos. 9,891,350 (Lofftus et al.) and 9,469,738 (Nair et al.),the disclosures of both of which are incorporated herein by reference.

The continuous polymeric binder of the (a) porous particles can also bederived from ethylenically unsaturated polymerizable monomers andpolyfunctional reactive compounds as described for example in U.S. Pat.No. 8,703,834 (noted above), the disclosure of which is incorporatedherein by reference.

In some embodiments, the continuous polymeric phase of the (a) porousparticles comprises one or more cellulose polymers, a polyester, apolystyrene, or a combination thereof.

In general, the (a) porous particles used in the present invention havea mode particle size equal to or less than 50 μm, or of at least 2 μmand up to and including 50 μm, or typically of at least 3 μm and up toand including 30 μm or even up to and including 40 μm. Most useful (a)porous particles have a mode particle size of at least 3 μm and up toand including 20 μm. Mode particle size represents the most frequentlyoccurring diameter for spherical particles and the most frequentlyoccurring largest diameter for the non-spherical particles in a particlesize distribution histogram, which can be determined using knownequipment (including light scattering equipment such as the Sysmex FPIA3000 Flow Particle Image Analyzer that used image analysis measurementsand that can be obtained from various sources including MalvernPanalytical; and coulter counters and other particle characterizingequipment available from Beckman Coulter Diagnostics), software, andprocedures.

Pore stabilizing materials such as hydrocolloids can be present withinat least part of the volume of the discrete pores distributed throughoutthe continuous polymeric phase, which pore stabilizing materials aredescribed in the Nair, Nair et al., and Putnam et al. patents citedabove. For example, the pore stabilizing hydrocolloids can be selectedfrom the group consisting of carboxymethyl cellulose (CMC), a gelatin orgelatin derivative, a protein or protein derivative, polyvinyl alcoholand its derivatives, a hydrophilic synthetic polymer, and awater-soluble microgel.

It can be desired in some embodiments to provide additional stability ofone or more discrete pores in the (a) porous particles during theirformation, by having one or more amphiphilic block copolymers disposedat the interface of the one or more discrete pores and the continuouspolymeric phase. Such materials are “low HLB”, meaning that they have anHLB (hydrophilic-lipophilic balance) value as it is calculated usingknown science, of 6 or less, or even 5 or less. The details of theseamphiphilic polymers and their use in the preparation of the (a) porousparticles are provided in U.S. Pat. No. 9,029,431 (Nair et al.), thedisclosure of which is incorporated herein by reference. A particularlyuseful amphiphilic block copolymer useful in such embodiments comprisespoly(ethyleneoxide) and poly(caprolactone) that can be represented asPEO-b-PCL. Amphiphilic block copolymers, graft copolymers and randomgraft copolymers containing similar components are also useful includingother polymeric emulsifiers such as GRINDSTED® PGPR 90, polyglycerolpolyricinolate emulsifier, obtained from Danisco, Dupont.

Such an amphiphilic copolymer can be generally present in the (a) porousparticles in an amount of at least 1 weight %, or at least 2 weight %and up to and including 50 weight %, based on total (a) porous particledry weight.

The (a) porous particles used in this invention can be spherical ornon-spherical depending upon the desired use. In a method used toprepare the (a) porous particles, additives (shape control agents) canbe incorporated into the first or second aqueous phases, or in the oil(organic) phase to modify the shape, aspect ratio, or morphology of the(a) porous particles, using known technology. The (a) porous particlescan also comprise surface stabilizing agents, such as colloidal silica,on the outer surface in an amount of at least 0.1 weight %, based on thetotal dry weight of the (a) porous particle.

The average size of the discrete pores in the (a) porous particles isdescribed above.

The (a) porous particles can be provided as powders, or as aqueoussuspensions (including water or water with water-miscible organicsolvents such as alcohols). Such powders and aqueous suspensions canalso include surfactants or suspending agents to keep the (a) porousparticles suspended or for rewetting them in an aqueous medium.

The (a) porous particles are generally present in a dry foamedopacifying layer in an amount of at least 0.1 weight % and up to andincluding 35 weight %, or typically at least 0.5 weight % and up to andincluding 25 weight %, or even at least 1 weight % and up to andincluding 20 weight %, based on the total weight of the dry foamedopacifying layer (including any residual aqueous medium), particularlywhen the (a) porous particles have a mode size of at least 3 μm and upto and including 20 μm.

In the dry foamed opacifying layer, the large mismatch in refractiveindex between the discrete pores of the (a) porous particles and thepolymer walls (continuous polymeric phase), causes incidentelectromagnetic radiation passing through the dry foamed opacifyinglayer to be scattered by the multiplicity of interfaces and discretepores. The back scattered electromagnetic radiation can again bescattered and returned in the direction of the incident electromagneticradiation thus reducing the attenuation and contributing to theopacifying power and brightness or luminous reflectance of the dryopacifying layer. If a small amount of (e) opacifying colorant ispresent in the (a) porous particles, for example either in the discretepores or in the continuous polymer phase of the (a) porous particles,the opacifying power of the dry foamed opacifying layer is increased.This is because the multiple scattering of electromagnetic radiation inthe dry foamed opacifying layer increases the path length of theelectromagnetic radiation through it, thereby increasing the chance thatthe electromagnetic radiation will encounter the (e) opacifying colorantand be blocked or absorbed by it.

(b) Binder Materials:

The aqueous foamed opacifying composition also contains one or more (b)binder materials to hold the (a) porous particles, (c) two or moreadditives, and (e) opacifying colorant together on the non-woven fabricafter the composition has been applied thereto. The one or more (b)binder materials can behave as a binding matrix for all the materials insuch wet compositions, and can form a (b′) matrix material to hold the(a) porous particles, (c) one or more additive, and (e) opacifyingcolorant(s) together in a dry foamed opacifying layer.

It is particularly useful that a (b) binder material have the followingproperties: (i) it is water-soluble or water-dispersible; (ii) it iscapable of being disposed onto a suitable substrate as described below;(iii) it is capable of being dried and at least partially crosslinked(or at least partially cured); (iv) it has good light and heatstability; and (v) it is film-forming but contributes to the flexibilityof the laminate precursor (and later laminated decorative article) andis thus not too brittle, for example generally having a glass transitiontemperature (T_(g)) of less than 25° C., or of less than 0° C., or ofless than or equal to −10° C., or of less than or equal to −25° C., asdetermined using Differential Scanning Calorimetry.

The choice of (b) binder materials can also be used to optimize a (b′)matrix material in the dry formulation of all of the (a), (c), and (e)materials described herein, to provide desired properties. For example,the (b) binder material can be used to provide a (b′) matrix materialthat adds to a supple feel to touch and a flexibility desired, forexample, for hanging draperies. The (b′) matrix material derived fromthe (b) binder material upon its at least partial and possibly, fullcuring or crosslinking.

The (b) binder material can include one or more organic polymers thatare film forming and that can be provided as an emulsion, dispersion, orin an aqueous solution, and that cumulatively provide the propertiesnoted above. It can also include one or more polymers that areself-crosslinking or self-curable, or it can include one or morepolymers that are self-crosslinking or self-curable, or it can includeone or more polymers to which crosslinking agents are added and are thuscurable or capable of being at least partially crosslinked underappropriate conditions.

For example, if the (b) binder material comprises a crosslinkable (orcurable) polymer in the presence of a suitable crosslinking or curingagent or catalyst, such crosslinking (or curing) can be activatedchemically with heat, radiation, or other known means. A curing orcrosslinking process serves to provide improved insolubility of theresulting dry foamed opacifying layer as well as cohesive strength andadhesion to the substrate. The curing or crosslinking agent is generallya chemical having functional groups capable of reacting with reactivesites in a (b) binder material (such as a functionalized latex polymer)under curing conditions to thereby produce a crosslinked structure.Representative crosslinking agents include but are not limited to,multi-functional aziridines, aldehydes, methylol derivatives, andepoxides.

Useful (b) binder materials include but are not limited, to poly(vinylalcohol), poly(vinyl pyrrolidone), ethylene oxide polymers,polyurethanes, urethane-acrylic copolymers, other acrylic polymers,styrene-acrylic copolymers, vinyl polymers, styrene-butadienecopolymers, acrylonitrile copolymers, and polyesters, silicone polymersor a combination of two or more of these organic polymers. Such (b)binder materials are readily available from various commercial sourcesor they can be prepared using known starting materials and syntheticconditions. The (b) binder material can be anionic, cationic or nonionicin total charge. A useful class of film-forming (b) materials includesaqueous latex polymer dispersions such as acrylic latexes that can beionic or nonionic colloidal dispersions of acrylate polymers andcopolymers. Useful film-forming aqueous latexes includestyrene-butadiene latexes, poly(vinyl chloride) and poly(vinylidenechloride) latexes, poly(vinyl pyridine) latexes, poly(acrylonitrile)latexes, and latexes formed from acrylonitrile, butyl acrylate, andethyl acrylate.

The one or more (b′) matrix materials derived from one or more (b)binder materials, can be present in the dry foamed opacifying layer inan amount of at least 10 weight % and up to and including 80 weight %,or typically at least 20 weight % and up to and including 60 weight %,based on the total dry foamed opacifying layer (that is, the totalweight of all components including any residual solvent).

It is useful that the dry weight ratio of the (a) porous particles tothe (b′) matrix material in the dry foamed opacifying layer is at least2:3 and up to and including 9:1, and more likely at least 1:1 and up toand including 3:1.

(c) Two or more Additives:

The dry foamed opacifying layer used in the present invention canfurther include (c) two or more additives in an amount of at least0.0001 weight % and up to and including 50 weight % and typically atleast 1 weight % and up to and including 45 weight %, based on the totalweight of the dry foamed opacifying layer (including any residualaqueous medium). These amounts refer to the total amounts of the (c) twoor more additives, not to each additive individually.

Such (c) two or more additives include materials such as dispersants,foaming surfactants, foam stabilizers, plasticizers, fire retardants,biocides (such as fungicides and antimicrobials), preservatives,thickeners, pH buffers, thickeners, and inert inorganic and organicfillers that are not inorganic or organic pigments (colorants). Therecan be mixtures of each type of the (c) two or more additives ormixtures of two or more types of (c) two or more additives in each dryopacifying layer. It is particularly useful in most dry foamedopacifying layers to include at least one foaming surfactant and atleast one foam stabilizer, and representative materials are definedbelow.

Such (c) two or more additives are different from the (e) opacifyingcolorants (described below) because individually or collectively, theywill not substantially block or absorb incident electromagneticradiation in the wavelength range of at least 380 nm and up to andincluding 800 nm, as determined in the manner described above for the(e) opacifying colorant.

Any of these (c) two or more additives thereof can be present within anylocation of the dry foamed opacifying layer, including but not limitedto: the continuous polymeric phase of the (a) porous particles; a volumeof some or all the discrete pores of the (a) porous particles; or boththe volume of the discrete pores and the continuous polymeric phase ofthe (a) porous particles. Alternatively, such (c) two or more additivescan be present in the (b) binder material alone, or in both the (b)binder material and in the (a) porous particles.

It would also be understood that while such (c) two or more additivescan be in the dry foamed opacifying layer, and the same or different (c)two or more additives can be also present in the non-woven fabric ordecorative fabric described above. Thus, any of the (c) two or moreadditives can be present in the same or different amounts in multiplelocations in the laminate precursor roll prepared according to thepresent invention.

The “inert” inorganic or organic fillers useful as (c) two or moreadditives are particles that can be added to reduce the use of moreexpensive (b) binder materials. Such inert materials do not undergo achemical reaction in the presence of water or other components in anaqueous foamed opacifying composition (described below); nor do theyabsorb electromagnetic radiation like the (e) opacifying colorants.Useful inert organic or inorganic filler materials include but are notlimited to titanium dioxide, talc, clay (for example, kaolin), magnesiumhydroxides, aluminum hydroxides, dolomite, glass beads, silica, mica,glass fibers, nano-fillers, calcium carbonate, and combinations thereof.

At least one of the (c) two or more additives is a surfactant that isdefined as a compound that reduces surface tension in an aqueousformulation composition. In most embodiments, this essential surfactantis a foaming agent that functions to create and enhance foam formation.In many such embodiments, the (c) two or more additives comprise one ormore foaming agents (or foaming surfactants) as well as one or more foamstabilizing agents (or foam stabilizers) that are also surface activeagents that function to structure and stabilize the foam. Examples ofuseful foaming agents (foaming surfactants) that are also surface-activeagents, and foam stabilizers include but are not limited to, ammoniumstearate, ammonium palmitate, sodium lauryl sulfate, ammonium laurylsulfate, ammonium or sodium alkyl sulfosuccinate, disodium stearylsulfosuccinate, diammonium n-octadecyl sulfosuccinamate, ethoxylatedalcohols, ionic or nonionic agents such as fatty acid soaps or a fattyacid condensation product with an alkaline oxide, for example, thecondensation product of ethylene oxide with lauryl or oleic acid or anester of fatty acids and similar materials, many of which can beobtained from various commercial sources. Mixtures of foaming agents canbe used if desired. Some of the noted compounds also act as foamstabilizers, but it best to use both a foaming surfactant (agent) and afoam stabilizer together for synergistic effects of foaming andstabilization.

The relative amounts of each of the foaming surfactants and foamstabilizers is not critical as long as the desired functions areevident, that is suitable foaming properties as required to prepare anaqueous foamed opacifying composition, and stability of that aqueousfoamed opacifying composition during storage and manufacture of thelaminate precursors described herein. The optimal amounts of each ofthese (c) two or more additives can be determined by using routineexperimentation and the teaching provided herein.

Useful biocides (that is, antimicrobial agents and antifungal agents)that can be present as (c) two or more additives and can include but arenot limited to, silver particles, platelets, or fibrous strands, andsilver-containing compounds such as silver chelates and silver saltssuch as silver sulfate, silver nitrate, silver chloride, silver bromide,silver iodide, silver iodate, silver bromate, silver tungstate, silverphosphate, and silver carboxylates. In addition, copper particles,platelets, or fibrous strands and copper-containing compounds such ascopper chelates and copper salts can be present as (c) two or moreadditives for biocidal purposes.

It can also be useful to include thickeners as (c) two or more additivesin order to modify the viscosity of the aqueous foamed opacifyingcomposition and to control its rheology.

In some embodiments, the (c) two or more additives further comprises oneor more of an antimicrobial agent, a fire retardant, or both anantimicrobial agent and a fire retardant.

(d) Aqueous Medium:

After the aqueous foamed opacifying composition (described below) hasbeen applied to the back side of the non-woven fabric and dried,residual aqueous medium including water or auxiliary solvents (describedbelow) in the dry foamed opacifying layer is desirably less than 5weight %, or even less than 2 weight %, of the total dry foamedopacifying layer weight.

(e) Opacifying Colorants:

The use of (e) opacifying colorants in a dry foamed opacifying layer isdesirable to block or absorb incident electromagnetic radiation withinthe range of wavelengths of at least 380 nm and up to and including 800nm. The (e) opacifying colorants can be water-soluble dyes orwater-dispersible pigments, or combinations of each or both types ofmaterials. The amount of electromagnetic radiation that can be blockedor absorbed by an (e) opacifying colorant can be determined by measuringopacity of an applied composition as described below. The (e) opacifyingcolorant can be a single colorant or a combination of materials thatcollectively act as the “opacifying colorant.”

In many embodiments, the (c) opacifying colorant can be present withinthe (a) porous particles, for example, within a volume of at least some,if not all, discrete pores within the (a) porous particles orincorporated within the continuous polymeric binder of the (a) porousparticles, or within both the volume of discrete pores and thecontinuous polymeric binder of the (a) porous particles.

This is highly advantageous as the (a) porous particles can be used to“encapsulate” various (e) opacifying colorants as well as some or all ofthe (c) two or more additives (described below) so they are keptisolated from the other components of the dry foamed opacifying layer.For example, the (e) opacifying colorant can be located solely withinthe (a) porous particles. In other embodiments, it can be useful toincorporate (e) opacifying agents solely or additionally within the (b)binder material in which the (a) porous particles are dispersed.

While the (e) opacifying colorants can provide some coloration ordesired hue, they are not purposely chosen for this purpose and are thusmaterials that are chosen to be different from the tinting colorantsdescribed herein as (c) two or more additives or for the anti-blockingmaterial.

Examples of (e) opacifying colorants that can be used individually or incombination include but are not limited to, neutral or black pigments ordyes (other than a carbon black), carbon black, black iron oxide,graphite, aniline black, anthraquinone black, or combinations thereof,and combinations of colored pigments or dyes such as cyan, magenta,yellow, green, orange, blue, red and, violet dyes. The present inventionis not limited to only the specific (e) opacifying colorants describedherein but these are considered as suitable guidance for a skilledworker to devise other combinations of (e) opacifying colorants for thedesired absorption in a chosen range of electromagnetic radiation. Acarbon black or neutral or black pigment or dye other than a carbonblack, of which there are many types available from commercial sources,is particularly useful as an (e) opacifying colorant.

The (e) opacifying colorant can be generally present in the dry foamedopacifying layer in an amount of at least 0.002 weight % and up to andincluding 2 weight %, or even at least 0.02 weight % and up to andincluding 1 weight %, all based on the total weight of the dry foamedopacifying layer (including any aqueous medium). As mixtures of thematerials can be used if desired, these amounts also refer to the totalamount of a mixture of materials used as the (e) opacifying colorant. Asnoted above, an (e) opacifying colorant can comprise a combination oftwo or more component materials (such as a combination of dyes or acombination of pigments) designed in hues and amounts so that thecombination meets the desired black-out and coloration propertiesdescribed herein.

In some embodiments, the (e) opacifying colorants, if in pigment form,are generally milled to a fine particle size and then encapsulatedwithin the volume of the discrete pores of the (a) porous particles byincorporating the milled pigment within an aqueous phase used in makingthe (a) porous particles. Alternatively, the (e) opacifying colorant canbe incorporated within the continuous polymeric phase of the (a) porousparticles by incorporating the (e) opacifying colorant in the oil phaseused in making the (a) porous particles. Such arrangements can beachieved during the manufacture of the (a) porous particles using theteaching provided herein and the teaching provided in references citedabove for making the (a) porous particles.

In some embodiments, it can be useful to incorporate at least 95% (byweight) of the total (e) opacifying colorant within the volume of the(a) porous particles (either in the discrete pores, continuous polymericphase, or both), and to incorporate the remainder, if any, within the(b) binder material.

However, in many other embodiments, 100% of the (e) opacifying colorantis incorporated within the (a) porous particles. For example, more than50% of the total (e) opacifying colorant can be disposed or incorporatedwithin the continuous polymeric phase of the (a) porous particles, andthe remainder can be incorporated within the volume of the discretepores. Alternatively, all the (e) opacifying colorant can beincorporated into the volume of the discrete pores.

Aqueous Foamable Opacifying Compositions

The dry foamed opacifying layers formed according to the presentinvention can be provided from corresponding aqueous foamed opacifyingcompositions that can be prepared using the materials and proceduresdescribed below.

The essential (a) through (e) components described above are generallypresent in an (d) aqueous medium in amounts different from the amountsdefined above for the dry foamed opacifying layer. However, the relativepercentages (proportions) of the components in the aqueous foamedopacifying composition generally should be the same as in the dry foamedopacifying layer.

The amounts of the components in the aqueous foamable opacifyingcomposition and the aqueous foamed opacifying composition areessentially the same as foaming does not appreciably change the % solidsor amounts of each component.

For example, the (a) porous particles (as described above) can bepresent in an aqueous foamed opacifying composition in an amount of atleast 0.05 weight % and up to and including 20 weight %, or typically ofat least 0.5 weight % and up to and including 15 weight %, all based onthe total weight of the aqueous foamed opacifying composition. Such (a)porous particles generally have a mode particle size of at least 2 μmand up to and including 50 μm and a porosity of at least 20 volume % andup to and including 70 volume %.

One or more (b) binder materials (as described above) can be present inthe aqueous foamed opacifying composition in an amount of at least 15weight % and up to and including 70 weight % or typically of at least 30weight % and up to and including 50 weight %, all based on the totalweight of the aqueous foamed opacifying composition.

The (c) two or more additives (as described above) can be present in theaqueous foamed opacifying composition in an amount of at least 0.0001weight % and up to and including 30 weight % or typically of at least0.001 weight % and up to and including 20 weight %, all based on thetotal weight of the aqueous foamed opacifying composition. At least oneof such (c) two or more additives is a foaming surfactant (as describedabove) and another is a foam stabilizer (as described above). Theseamounts refer to the total of all of the (c) two or more additives, notto each additive individually.

The one or more (e) opacifying colorants (as described above) can bepresent in the aqueous foamed opacifying composition in an amount of atleast 0.0001 weight % or at least 0.003 weight % and up to and including0.5 weight %, or even in an amount of least 0.003 weight % and up to andincluding 0.2 weight % especially when the opacifying colorant is acarbon black, all based on the total weight of the aqueous foamedopacifying composition.

Water is the predominant solvent used in an (d) aqueous medium in theaqueous formulations. By “predominant” is meant that of the total weightof solvents in the (d) aqueous medium, water comprises at least 75weight %, and more likely at least 80 weight % and up to and including100 weight %, of the total solvent weight. Auxiliary solvents that canbe present must not adversely affect or harm the other components in theaqueous formulation. Such auxiliary solvents can be water-miscibleorganic solvents such as alcohols and ketones.

The aqueous medium can comprise at least 30 weight % and up to andincluding 70 weight %, or typically at least 40 weight % and up to andincluding 60 weight %, of the total aqueous foamed opacifyingcomposition weight.

All (a), (b), (c), and (e) components can be suitably mixed in an (d)aqueous medium by dispersing with a cowles blade. Representative timeand temperature conditions for making such aqueous foamed opacifyingcompositions would be readily apparent to one skilled in the art.

Making Laminate Precursors

According to the present invention, laminate precursors, in rolled form,can be independently provided (step A) from one or more differentnon-woven fabrics, as described above, each having a face side and aback side. The face side is considered the side of the non-woven fabricthat is viewable and left uncovered. A skilled worker can decide which“side” is best for application of the aqueous foamed opacifyingcomposition. For example, the worker may choose the back side as theless aesthetically appealing side of the non-woven fabric and then theopposing side that has the nicer touch or color may be chosen as theface side.

The dry foamed opacifying layer provided in each laminate precursortypically comprises (a) porous particles, a (b′) matrix material, (c)two or more additives, an (e) opacifying colorant, and possibly someresidual (d) aqueous medium, all of which are described in more detailabove.

Previously to or in combination with step A) according to the presentinvention, an aqueous foamed opacifying composition can be formed byappropriate foaming or aerating a corresponding aqueous foamableopacifying composition that has basically the same materials andcomponent concentration.

Thus, the aqueous foamable opacifying composition can be aerated toprovide an aqueous foamed opacifying composition having a foam densityof at least 0.1 g/cm³ and up to and including 0.5 g/cm³, or of at least0.15 g/cm³ and up to and including 0.4 g/cm³, or even of at least 0.15g/cm³ and up to and including 0.27 g/cm³. This aeration procedure can becarried out using suitable conditions and equipment that would bereadily apparent to one skilled in the art in order to create a “foam,”for example in the presence of a foaming surfactant and foam stabilizerthat are present at least within the (c) two or more additives describedabove. For example, aeration can be carried out by mechanicallyintroducing air or an inert gas (such as nitrogen or argon) in acontrolled manner. High shear mechanical aeration can be carried outusing sonication or high-speed mixers, such as those equipped with acowles blade, or with commercially available rotorstator mixers withinterdigitated pins such as an Oakes mixer or a Hobart mixer, byintroducing air under pressure or by drawing atmospheric air into theaqueous foamable opacifying composition with the whipping action of themixer. Suitable foaming equipment can be used in a manner to provide thedesired foam density with modest experimentation. It can be useful tochill or cool the aqueous foamable opacifying composition below ambienttemperature to increase stability by increasing composition viscosity,and to prevent its collapse. This chilling operation can be carried outimmediately before, immediately after, or during the aeration procedure.Stability of the resulting aqueous foamed opacifying composition canalso be enhanced by the presence of the foam stabilizer agent as one ofthe (c) two or more additives.

Onto the back side of one of more of these non-woven fabrics, an aqueousfoamed opacifying composition described above can be applied (step B) toprovide an applied coating or layer of that aqueous foamed opacifyingcomposition. The wet coverage of the applied aqueous foamed opacifyingcompositions can be the same or different on the one or more differentnon-woven fabrics, that upon drying, can provide the desired drycoverage as described herein.

Each aqueous foamed opacifying composition can be applied using asuitable application means and in any suitable manner. For example, thenon-woven fabric can be coated with an aqueous foamed opacifyingcomposition using a floating knife, hopper, blade, or gap coatingapparatus and appropriate coating procedures including but not limitedto blade coating, gap coating such as “knife-over-roll” and“knife-over-table” operation, floating knife, slot die coating, or slidehopper coating. Thus, the aqueous foamed opacifying composition can bedisposed directly onto a back side of the non-woven fabric wherein“directly” means there are no intervening or intermediate layers, or itcan be disposed indirectly onto the back side of the non-woven fabric,meaning that an interlayer of some type (primer or adhesive layer) canbe present.

The applied aqueous foamed opacifying composition can be dried (step C)to provide a dry coverage of less than or equal to 1000 g/m², andgenerally at least 50 g/m², or at least 100 g/m² and up to and including500 g/m² of a dry foamed opacifying layer having a light blocking value(LBV_(oc)) of at least 2, or at least 3. In reference to a dry foamedopacifying layer, the term “dry” means that the layer comprises theaqueous medium (described below) in an amount of less than 5 weight %,or even less than 2 weight %, based on the total weight of the dryfoamed opacifying layer. Drying operations to remove most or all of theaqueous medium can be achieved using suitable apparatus and treatmentswith heat or radiation that does not adversely affect the non-wovenfabric and the aqueous foamed opacifying composition. For example,drying can be accomplished by heating with warm or hot air, microwaves,or IR irradiation at a temperature and time sufficient for drying (forexample, at least 160° C.) to provide a dry foamed opacifying layer.

The drying step C) can also cause at least partial curing of the dryfoamed opacifying layer especially if curable or crosslinkable polymersand appropriate catalysts are present. For example, a curing orcrosslinking reaction can occur between reactive side groups of suitablecurable polymer chains in a functionalized self-crosslinking latexcomposition to form (b′) matrix material from the (b) binder material.If the chosen (b) binder material is not itself heat reactive, suitablecatalysts and curing (crosslinking) agents can be added to promotecuring or crosslinking.

Either between the B) applying step and the C) drying step, orimmediately after the C) drying step, an anti-blocking compositionformulation can be applied (step D) to each applied foamed opacifyingcomposition to form one or more corresponding laminate precursors havinganti-blocking material back side and a non-woven fabric face side. Theuse of an anti-blocking material according to the present invention isoptional but desirably in many embodiments. The one or more laminateprecursors can have the same or different non-woven fabrics, the same ordifferent applied foamed opacifying compositions, and the same ordifferent anti-blocking material.

Useful anti-blocking materials can be provided from an anti-blockingcomposition comprising one or more of organic or inorganic particles. Ananti-blocking material useful in the practice of this invention canprovide one or more functional properties but the primary function is tokeep the non-woven face side from sticking to the opposite side of therolled up laminate precursor.

Thus, the anti-blocking material can provide a “release” function wherethe coefficient of friction between the dry opacifying layer side of thelaminate precursor and any other solid surface such as the face side ofthe non-woven fabric, in rolled form, is reduced allowing easyseparation of the contacting surfaces; or an anti-blocking functionwhere microscopic protrusions or asperities help to minimize surfacecontact between the surfaces by increasing the distance between the twocontacting surfaces, thereby minimizing blocking.

Thus, the term “anti-blocking” does not refer to blocking of impingingradiation as in “light-blocking”, but refers to the function describedabove to keep one side of rolled articles sticking to the opposite side.

Before application, each anti-blocking composition formulation isprepared as an aqueous dispersion of the desired components. Forexample, in particularly useful embodiments, the anti-blockingcomposition formulation can comprise inorganic or organic spacerparticles in admixture with an organic polymeric binder, and acrosslinking agent for the (iv) organic polymeric binder, and if needed,an optional thickener and a coating aid including but not limited to awetting surfactant (having a hydrophilic-lipophilic balance number of atleast 7), all mixed together in water to form a stable aqueousdispersion.

As described below, an anti-blocking composition formulation can bedisposed over (for example, directly on) the applied foamed opacifyingcomposition in a uniform continuous manner to provide one or moreanti-blocking materials. In other embodiments, the anti-blockingmaterial formulation can be disposed in a discontinuous manner, in smallor large regions, for example, from spraying to form a regular orirregular pattern.

In some embodiments, the anti-blocking material formulation can befoamed similarly to foaming of the aqueous foamable opacifyingcomposition described above before it is applied.

The anti-blocking material can be present at a dry coverage of at least0.1 g/m² and up to and including 50 g/m² or of at least 5 g/m² and up toand including 25 g/m².

Useful inorganic or organic spacer particles generally have a modeparticle size of at least 1 μm, or of at least 2 μm and up to andincluding 100 μm, or up to and including 30 μm, or even at least 2 μmand up to and including 20 μm. Mode particle size can be determined asdescribed above for the definition of the sizes of (a) porous particles.

In addition, these inorganic or organic spacer particles are capable ofresisting melt flow at pressures up to and including 100 psi (689.5 kPa)and temperatures up to and including 220° C.

Useful inorganic or organic spacer particles can comprise natural orsynthetic silica; talc; clay; mica; calcium carbonate; nylon; glassparticles; a polytetrafluoroethylene, a crosslinked silicone basedorganic polymer, a poly(alkylsilylsesquioxane); a crosslinked styrenicpolymer or copolymer; a crosslinked acrylate or methacrylate polymer orcopolymer; a crosslinked acrylamide or methacrylamide polymer orcopolymer; a crosslinked allylic polymer or copolymer; or a combinationof two or more of these materials. Such materials can be obtained fromvarious commercial sources, or prepared using known procedures andstarting materials.

The inorganic or organic spacer particles can be present as ananti-blocking material at a dry coverage of at least 0.001 g/m² and upto and including 30 g/m², or at least 1 g/m² and up to and including 20g/m².

The anti-blocking composition formulation can also comprise an organicpolymeric binder in which the organic or inorganic spacer particles, andother components are dispersed. This organic polymeric binder can bewater-soluble or water-dispersible and can comprise one or morematerials. In addition, the organic polymeric binder can befilm-forming, that is, it can form a film once applied and dried. Suchmaterials can be self-crosslinkable and crosslinkable using a suitablecrosslinking agent as described below. Useful organic polymeric bindersinclude but are not limited to, film forming polymers such as apartially hydrolyzed polyvinyl acetate, poly(vinyl alcohol), poly(vinylpyrrolidone), cellulosic polymers (such as carboxymethyl cellulose andhydroxymethyl cellulose), a polysaccharide, a poly(ethylene oxide),acrylamide polymers, polyester ionomers, gelatin or gelatin derivatives,gellan, starches, polyethylene imine, polyvinyl amine, and derivativesof these materials, polyurethanes, urethane-acrylic copolymers, otheracrylic polymers, styrene-acrylic copolymers, vinyl polymers, andpolyesters, or a combination of two or more of these organic polymerbinders. Such organic polymeric binders are readily available fromvarious commercial sources or prepared using known starting materialsand synthetic conditions. The organic polymeric binder can be useful foradhering the organic or inorganic spacer particles and other notedcomponents onto the outer surface of the applied aqueous foamedopacifying composition.

The organic polymeric binder can be present in an amount of at least 1weight % and up to and including 90 weight %, or typically at least 5weight % and up to and including 75 weight %, based on the total dryapplied anti-blocking material formulation weight.

Additionally, it may be beneficial to chemically crosslink some organicpolymeric binders to improve cohesiveness. Such organic polymericbinders can be at least partially curable or crosslinkable, and can becured up to 100% of all potential curable or crosslinking sites. Theidentity and amount of a suitable crosslinking agent would be readilydetermined by a skilled worker and will depend on the choice of organicpolymeric binder and its reactivity with the crosslinking agent, thenumber of crosslinking sites available, compatibility with othercomponents, and manufacturing constraints such as formulation pot life,application means, and drying speed.

The anti-blocking composition formulation can be prepared using one ormore wetting surfactants or coating aids to aid in its coating ordeposition onto the applied aqueous foamed opacifying composition.

If the anti-blocking composition formulation is to be disposed byspraying, surfactants known in the art as spreading agents that arecapable of reducing the surface tension substantially to aid in theformation of small drops.

The applied anti-blocking composition formulation can include one ormore of various additives that provide various properties orcharacteristics, such as a biocide or antimicrobial agent of which thereare numerous materials known in the art for this purpose (includingsilver metal and silver salts); antistatic agents known in the art todissipate electrical charge and static; tactile modifiers, visualmodifiers that provide a matte, opalescent or other such desirable look;and soil resistance agents that reduce the potential for soiling fromhandling or spills.

If desired, the applied anti-blocking composition formulation in eachlaminate precursor can be partially or totally cured after the D)applying step and before the E) densifying step (described below), usingsuitable conditions, similarly to the C) drying step.

Subsequent to or simultaneously with the D) applying step, the dryfoamed opacifying layer is densified (or crushed) so that it will have athickness that is at least 20% less than its thickness beforedensifying. Densification or crushing is a process of subjecting the dryfoamed opacifying layer to mechanical pressure, to densify (reducefoamed volume) and to reduce composition thickness. This process can becarried out in any suitable manner but it is generally carried out by aprocess that provides pressure to the dry foamed opacifying layer, forexample, by passing the laminate precursor through a compressioncalendering operation, pressing operation, or embossing operation, or acombination thereof. For example, the laminate precursor can be pressedbetween flat plates or through nip rollers under pressure, or it can bepassed through a combination of calendering and embossing rollers toreduce the thickness of the dry foamed opacifying layer and to densifythe foam structure therein. This process can be considered a “densifyingoperation” as the dry foamed opacifying layer is made denser while it ispressed together. The thickness of the dry foamed opacifying layerbefore and after crushing (densifying) can be determined by a knowntechnique such as laser profilometry.

The crushing or densifying operation can be carried out at any suitabletemperature including room temperature (for example, 20-25° C.) and upto and including 90° C., or more likely at a temperature of at least 20°C. and up to and including 90° C. The crushing or densifying operationcan be carried out at nip pressures that are suitable for theconstruction of the non-woven fabric including the openness factor toprevent over crushing and consequent loss of uniform opacity of the dryfoamed opacifying layer. A useful crushing pressure can be determinedusing routine experimentation depending upon several factors includingthe dry foamed opacifying components and type and weight of non-wovenfabric used. For example, a useful crushing or densification pressurecan be at least 15 psi (103.4 kPa) and up to and including 200 psi (1379kPa).

Once densification is completed, each laminate precursor can be rolledup so that the anti-blocking material side is in contact with the faceside of the non-woven fabric, thereby providing one or more laminateprecursor rolls for immediate or future use.

Preparation of Laminated Decorative Articles

When a decorative fabric is provided with a face side and a back side(step G), one or more laminate precursor rolls can be unrolled (step H)and laminated, with the back side of the decorative fabric in contactwith the dry foamed opacifying layer of the unrolled laminate precursorroll. Under such laminating conditions, one or more laminatedlight-blocking decorative articles are formed. It is also possible thatthe G) laminating step includes further curing of the dry foamedopacifying layer in the unrolled laminate precursor roll.

One suitable technique includes the use of an adhesive material such asa thin intermediate heat seal or cold seal adhesive material between thedecorative fabric back side and the dry foamed opacifying layer of theunrolled laminate precursor roll. In some embodiments, the adhesivematerial is incorporated within the anti-blocking compositionformulation or within the aqueous foamed opacifying composition, orwithin both the anti-blocking composition formulation and the aqueousfoamed opacifying composition.

When using a heat seal adhesive, the laminate precursor can be suppliedfrom a suitable laminate precursor roll (for example, as a supply roll);the heat seal adhesive can be applied to one of the surfaces to beadhered; and then the unrolled laminate precursor and the decorativefabric from a suitable source (for example, a second supply roll) can bebrought together during lamination.

Alternatively or additionally, the heat seal adhesive can be supplied tothe back side of the decorative fabric and the two articles are broughttogether during lamination. In other embodiments, a heat seal adhesivecan be applied to both articles before they are brought together duringlamination. The heat seal adhesive also can be supplied (sprayed orsquirted) between the two articles as they are brought together. Theheat seal adhesive, after being heated, is then allowed to cool forexample to room temperature, followed by laminating the unrolledlaminate precursor and the decorative fabric.

Suitable adhesive materials are known in the art, and can comprise atleast one polyamide, polyester, epoxy resin, acrylic resin, anhydridemodified polyolefin, polyurethane, or blends of two or more types ofpolymers.

Other adhesive materials can be used in the present invention includingbut not limited to use of a layer of any cold seal orpressure-sensitive, photosensitive, or thermally-sensitive adhesiveprecursor material, followed by “activation” to create an adhesive layerusing pressure, photoexposure, or thermal exposure, respectively. Forexample, liquid adhesives can be used including plastisol, epoxy,acrylic, organosol, and urethane adhesives that can be applied to eitherthe laminate precursor roll with a suitable coating technique (gravurecylinder, knife, roller, reverse roller, or anilox roller) under heat,followed by cooling to secure the adhesive bond.

It is also possible to laminate the laminate precursor and thedecorative fabric without the use of an intermediate adhesive layer.This can be done in any suitable manner known in the art usingmechanical means without an adhesive means, using for example, directcalendar lamination to form a mechanical bond between the two articles.In direct calendar lamination, the two articles are brought together forexample, under heat from appropriate sources (for example, individualsupply rolls) and fed together into pressure rollers or a combination ofcalendar and embossing rollers to form the mechanical bonding uponcooling. The resulting laminated light-blocking decorative article canthen be taken up into a roll or otherwise stored or immediately used infinishing operations.

Alternatively or additionally, the face side of the non-woven fabric canbe modified with embossing or printing to provide a suitable image orpattern using known procedures such as inkjet printing or flexographicprinting, thereby forming printed images of text, pictures, symbols, orcombinations thereof. Such printed images can be visible, or they caninvisible to the unaided eye (for example, using fluorescent dyes in theprinted images). Alternatively, an outer surface can be covered bysuitable means with a colorless continuous or discontinuous layer toprovide a desired protective finish, or anti-microbial or soil releaseproperties. In many instances, the image formed in this manner, forexample, on an outer surface, is not visible or discernible from theother outer surface of the laminated light-blocking decorative article.

A thermally printed image can be formed on the face side of thenon-woven fabric or on the face side of the decorative fabric, forexample, by using a thermal (sublimable) dye transfer printing process(using heat and with or without pressure) from one or more thermal donorelements comprising a dye donor layer comprising one or more dyesublimation printable colorants. For example, a thermal colorant imagecan be obtained using one or more thermal dye patches (areas) with orwithout a thermal colorless (clear) patch (area). Useful details of sucha process are provided in U.S. Patent Application Publication2018/0327965 (Herrick et al.), the disclosure of which is incorporatedherein by reference.

In some embodiments, the laminated light-blocking decorative articleprepared according to this invention is a blackout drapery exhibiting astiffness of less than 15 mN, as measured by L&W bending force asmeasured using a L&W bending force test and an L&W Bending Testerapparatus (Lorentzen and Wettre Products).

In other embodiments, a laminated light-blocking decorative articleprepared according to this invention can be a blackout shade fabricexhibiting a stiffness of at least 15 mN, as measured by L&W bendingforce test and apparatus noted above.

For example, a laminated light-blocking decorative article preparedaccording to this invention can be a window shade having coloration,blackout, feel, and other properties desired by the customer.

The present invention provides at least the following embodiments andcombinations thereof, but other combinations of features are consideredto be within the present invention as a skilled artisan would appreciatefrom the teaching of this disclosure:

1. A method comprising, in order:

-   -   A) independently providing one or more different non-woven        fabrics, each non-woven fabric having a face side and a back        side;    -   B) applying an aqueous foamed opacifying composition to the back        side of the one or more different non-woven fabrics, the wet        coverage of the applied aqueous foamed opacifying composition        being the same or different on each of the one or more different        non-woven fabrics;    -   C) drying each applied aqueous foamed opacifying composition to        provide a dry coverage of less than or equal to 1000 g/m² of a        dry foamed opacifying layer having a light blocking value        (LBV_(oc)) of at least 2;    -   D) optionally, either between the B) applying step and the C)        drying step, or immediately after the C) drying step, applying        an anti-blocking material to each applied aqueous foamed        opacifying composition to form one or more laminate precursors        having an anti-blocking material back side and a non-woven        fabric face side, the one or more laminate precursors comprising        one or more different non-woven fabrics on its face side and the        same or different dry coverage of applied aqueous foamed        opacifying composition on the anti-blocking material back side;    -   E) simultaneously with or subsequent to the optional D) applying        step, densifying the dry foamed opacifying layer so that it will        have a thickness that is at least 20% less than its thickness        before densifying;    -   F) rolling up each of the one or more laminate precursors, to        provide one or more laminate precursor rolls,        -   wherein the aqueous foamed opacifying composition has at            least 35% and up to and including 70% solids and a foam            density of at least 0.1 g/cm³ and up to and including 0.5            g/cm³, and comprises:        -   (a) porous particles in an amount of at least 0.05 weight %            and up to and including 20 weight % of porous particles,            each porous particle comprising a continuous polymeric phase            and discrete pores dispersed within the continuous polymeric            phase, the porous particles having a mode particle size of            at least 2 μm and up to and including 50 μm and a porosity            of at least 20 volume % and up to and including 70 volume %;        -   (b) a binder material in an amount of at least 1520 weight %            and up to and including 70 weight % of a binder material,        -   (c) two or more additives in an amount of at least 0.0001            weight % and up to and including 30 weight %, the two of one            or more additives comprising at least one foaming surfactant            and at least one foam stabilizer,        -   (d) an aqueous medium, and        -   (e) an opacifying colorant in an amount of at least 0.0001            weight % and up to and including 0.5 weight %, which of an            opacifying colorant being that is a different material from            the (a) porous particles, (b) binder material, and (c) two            or more additives, and which opacifying colorant absorbs            electromagnetic radiation having a wavelength of at least            380 nm and up to and including 800 nm,        -   all amounts of (a) porous particles, (b) binder            material, (c) two or more additives, and (e) opacifying            colorant being based on the total weight of the aqueous            foamed opacifying composition.

2. The method of embodiment 1, wherein the optional D) step is carriedout, so that when the one or more laminate precursors are rolled up, theanti-blocking material side is in contact with the face side of thenon-woven fabric.

3. The method of embodiment 1, further comprising:

-   -   G) providing a decorative fabric having a face side and a back        side; and    -   H) unrolling a laminate precursor roll from the one or more        laminate precursor rolls and laminating the back side of the        decorative fabric to the dry foamed opacifying layer of the        unrolled laminate precursor roll,        -   to form a laminated light-blocking decorative article.

4. The method of embodiment 2, comprising:

-   -   G) providing a decorative fabric having a face side and a back        side; and    -   H) unrolling a laminate precursor roll from the one or more        laminate precursor rolls and laminating the back side of the        decorative fabric to the ani-blocking material back side of the        unrolled laminate precursor roll, to form a laminated        light-blocking decorative article.

5. The method of any of embodiments 1 to 4, wherein the dry foamedopacifying layer is subjected in the E) densifying step to adensification pressure of at least 15 psi (103.4 kPa) at a temperatureof at least 20° C. and up to and including 90° C.

6. The method of any of embodiments 3 to 5, wherein the H) laminatingstep includes curing the dry foamed opacifying layer in the unrolledlaminate precursor roll.

7. The method of any of embodiments 1 to 6, wherein the C) drying stepincludes curing the applied aqueous foamed opacifying composition.

8. The method of any of embodiments 2 and 4 to 7, further comprising:after the D) applying step, and before the E) densifying step, curingthe applied anti-blocking material.

9. The method of any of embodiments 1 to 8, further comprising:

-   -   before the A) providing step, forming the aqueous foamed        opacifying composition by aerating an aqueous foamable        opacifying composition to have a foam density of at least 0.1        g/cm³ and up to and including 0.5 g/cm³.

10. The method of embodiment 9, comprising aerating the aqueous foamableopacifying composition while it is chilled at a temperature belowambient temperature.

11. A laminate precursor roll comprising a non-woven fabric having aface side and a back side, a dry foamed opacifying layer that isdisposed on the back side of the non-woven fabric, and a non-blockingcomposition disposed on the dry foamed opacifying layer,

-   -   wherein the face side of the non-woven fabric is rolled up in        contact with the non-blocking composition, and    -   the dry foamed opacifying layer being present at a dry coverage        of less than or equal to 1000 g/m², and comprising:        -   (a) porous particles in an amount of at least 0.1 weight %            and up to and including 35 weight %, each porous particle            comprising a continuous polymeric phase and discrete pores            dispersed within the continuous polymeric phase, the porous            particles having a mode particle size of at least 2 μm and            up to and including 50 μm and a porosity of at least 20            volume % and up to and including 70 volume %;        -   (b′) a matrix material that is derived from a (b) binder            material having a glass transition temperature (T_(g)) of            less than 25° C., which (b′) matrix material is present in            an amount of at least 10 weight % and up to and including 80            weight %,        -   (c) two or more additives in an amount of at least 0.0001            weight % and up to and including 50 weight %, the two or            more additives comprising at least one foaming surfactant            and at least one foam stabilizer,        -   (d) an aqueous medium in an amount of less than 5 weight %,            and        -   (e) an opacifying colorant in an amount of at least 0.002            weight % and up to and including 2 weight %, which            opacifying colorant being a different material from the (a)            porous particles, (b′) matrix material, and (c) two or more            additives, and which opacifying colorant absorbs            electromagnetic radiation having a wavelength of at least            380 nm and up to and including 800 nm,        -   all amounts of (a) porous particles, (b′) matrix            material, (c) two or more additives, (d) aqueous medium,            and (e) opacifying colorant being based on the total weight            of the dry foamed opacifying layer.

12. Any of embodiments 1 to 11, wherein the one or more differentnon-woven fabrics is a blended or nonblended fabric.

13. Any of embodiments 1 to 12, wherein the one or more differentnon-woven fabrics is a spunlaced non-woven fabric.

14. Any of embodiments 1 to 13, wherein the one or more differentnon-woven fabrics has a basis weight of at least 0.5 oz/yd² (16.95g/m²).

15. Any of embodiments 1 to 14, wherein the one or more differentnon-woven fabrics has a basis weight of up to and including 25 oz/yd²(847.7 g/m²).

16. Any of embodiments 3 to 15, wherein the one or more differentdecorative fabrics is a woven fabric that is patterned or printed.

17. Any of embodiments 3 to 16, wherein the decorative fabric is a wovenfabric having a repeating design pattern that is woven or embroideredinto the decorative fabric.

18. Any of embodiments 3 to 17, wherein the decorative fabric is adouble cloth jacquard.

19. Any of embodiments 1 to 18, wherein either the one or more differentnon-woven fabrics or the decorative fabric, or both the one or moredifferent non-woven fabrics and the decorative fabric, comprise anantimicrobial agent, a fire retardant, or a soil release agent, or anycombination thereof.

20. Any of embodiments 3 to 19, wherein the laminated light-blockingdecorative article is a blackout drapery exhibiting a stiffness of lessthan 15 mN, as measured by L&W bending force.

21. Any of embodiments 3 to 19, wherein the laminated light-blockingdecorative article is a blackout shade fabric exhibiting a stiffness asmeasured by L&W bending force of at least 15 mN.

22. Any of embodiments 3 to 21, wherein the laminated light-blockingdecorative article is a window shade.

23. Any of embodiments 1 to 22, wherein the anti-blocking materialcomprises one or more organic or inorganic particles.

24. Any of embodiments 1 to 23, wherein the (e) opacifying colorant ispresent in the aqueous foamed opacifying composition in an amount of atleast 0.001 weight % and up to and including 0.3 weight %, based on thetotal weight of the aqueous foamed opacifying composition.

25. Any of embodiments 1 to 24, wherein the (e) opacifying colorant ispresent in the aqueous foamed opacifying composition in an amount of atleast 0.003 weight % and up to and including 0.5 weight %, based on thetotal weight of the aqueous foamed opacifying composition.

26. Any of embodiments 1 to 25, wherein the (e) opacifying colorant is acarbon black, a neutral black pigment or a dye other than a carbonblack, or a combination of two or more of such materials.

27. Any of embodiments 1 to 26, wherein the (e) opacifying colorant islocated solely in the (a) porous particles.

28. Any of embodiments 1 to 27, wherein the aqueous foamed opacifyingcomposition further comprises an adhesive material.

29. Any of embodiments 1 to 28, wherein the (c) two or more additivesfurther comprise one or more of an antimicrobial agent, a fireretardant, or both an antimicrobial agent and a fire retardant.

30. Any of embodiments 1 to 29, wherein the (c) two or more additivesfurther comprise one or more of dispersants, plasticizers, opticalbrighteners, thickeners, biocides, tinting colorants, inert inorganic ororganic fillers, or a combination of any of these materials.

31. Any of embodiments 1 o 30, wherein the (b) binder material has aglass transition temperature (T_(g)) of less than 25° C.

32. Any of embodiments 1 to 31, wherein the continuous polymeric phaseof the (a) porous particles comprises one or more cellulose polymers, apolyester, a polystyrene, or a combination thereof.

33. Any of embodiments 1 to 32, wherein the (b) binder materialcomprises a crosslinkable material and a curing agent.

34. Any of embodiments 1 to 33, wherein the at least one foamingsurfactant and the at least one foam stabilizer are independently one ofthe following compounds, or a mixture thereof: ammonium stearate,ammonium palmitate, sodium lauryl sulfate, ammonium lauryl sulfate,ammonium or sodium alkyl sulfosuccinate, disodium stearylsulfosuccinate, diammonium n-octadecyl sulfosuccinamate, ethoxylatedalcohols, a fatty acid soap, and a fatty acid condensation product withan alkylene oxide.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be achieved within the spirit and scopeof the invention.

The invention claimed is:
 1. A method comprising, in order: A)independently providing one or more different non-woven fabrics, eachnon-woven fabric having a face side and a back side; B) applying anaqueous foamed opacifying composition to the back side of the one ormore different non-woven fabrics, the wet coverage of the appliedaqueous foamed opacifying composition being the same or different oneach of the one or more different non-woven fabrics; C) drying eachapplied aqueous foamed opacifying composition to provide a dry coverageof less than or equal to 1000 g/m² of a dry foamed opacifying layerhaving a light blocking value (LBV_(oc)) of at least 2; D) optionally,either between the B) applying step and the C) drying step, orimmediately after the C) drying step, applying an anti-blockingcomposition formulation to each applied aqueous foamed opacifyingcomposition to form one or more laminate precursors having ananti-blocking composition back side and a non-woven fabric face side,the one or more laminate precursors comprising one or more differentnon-woven fabrics on its face side and the same or different drycoverage of applied aqueous foamed opacifying composition on theanti-blocking composition back side; E) simultaneously with orsubsequent to the optional D) applying step, densifying the dry foamedopacifying layer so that it will have a thickness that is at least 20%less than its thickness before densifying; F) rolling up each of the oneor more laminate precursors, to provide one or more laminate precursorrolls, wherein the aqueous foamed opacifying composition has at least35% and up to and including 70% solids and a foam density of at least0.1 g/cm³ and up to and including 0.5 g/cm³, and comprises: (a) porousparticles in an amount of at least 0.05 weight % and up to and including20 weight %, each porous particle comprising a continuous polymericphase and discrete pores dispersed within the continuous polymericphase, the porous particles having a mode particle size of at least 2 μmand up to and including 50 μm and a porosity of at least 20 volume % andup to and including 70 volume %; (b) a binder material in an amount ofat least 15 weight % and up to and including 70 weight %, (c) two ormore additives in an amount of at least 0.0001 weight % and up to andincluding 30 weight %, the two or more additives comprising at least onefoaming surfactant and at least one foam stabilizer, (d) an aqueousmedium, and (e) an opacifying colorant in an amount of at least 0.0001weight % and up to and including 0.5 weight %, which opacifying colorantbeing different materials from the (a) porous particles, (b) bindermaterial, and (c) two or more additives, and which opacifying colorantabsorbs electromagnetic radiation having a wavelength of at least 380 nmand up to and including 800 nm, all amounts of (a) porous particles, (b)binder material, (c) two or more additives, and (e) opacifying colorantbeing based on the total weight of the aqueous foamed opacifyingcomposition.
 2. The method of claim 1, wherein the optional D) applyingstep is carried out, so that when the one or more laminate precursorsare rolled up, the anti-blocking composition back side is in contactwith the face side of a non-woven fabric.
 3. The method of claim 1,further comprising: G) providing a decorative fabric having a face sideand a back side; and H) unrolling a laminate precursor roll from the oneor more laminate precursor rolls and laminating the back side of thedecorative fabric to the dry foamed opacifying layer of the unrolledlaminate precursor roll, to form a laminated light-blocking decorativearticle.
 4. The method of claim 2, further comprising: G) providing adecorative fabric having a face side and a back side; and H) unrolling alaminate precursor roll from the one or more laminate precursor rollsand laminating the back side of the decorative fabric to theanti-blocking material back side of the unrolled laminate precursorroll, to form a laminated light-blocking decorative article.
 5. Themethod of claim 1, wherein the dry foamed opacifying layer is subjectedin the E) densifying step to a densification pressure of at least 15 psi(103.4 kPa) at a temperature of at least 20° C. and up to and including90° C.
 6. The method of claim 3, wherein the H) laminating step includescuring the dry foamed opacifying layer in the unrolled laminateprecursor roll.
 7. The method of claim 1, wherein the C) drying stepincludes curing the applied aqueous foamed opacifying composition. 8.The method of claim 1, further comprising: before the A) providing step,forming the aqueous foamed opacifying composition by aerating an aqueousfoamable opacifying composition to have a foam density of at least 0.1g/cm³ and up to and including 0.5 g/cm³.
 9. The method of claim 1,wherein the one or more different non-woven fabrics is a blended fabric.10. The method of claim 1, wherein the one or more different non-wovenfabrics is a spunlaced non-woven fabric.
 11. The method of claim 3,wherein the decorative fabric is a woven fabric that is patterned orprinted.
 12. The method of claim 3, wherein the decorative fabric is awoven fabric having a repeating design pattern that is woven orembroidered into the decorative fabric.
 13. The method of claim 3,wherein the decorative fabric is a double cloth jacquard.
 14. The methodof claim 1, wherein the anti-blocking composition formulation comprisesone or more of organic or inorganic particles.
 15. The method of claim3, wherein either the one or more different non-woven fabrics or thedecorative fabric, or both the one or more different non-woven fabricsand the decorative fabric, comprise an antimicrobial agent, a fireretardant, or a soil release agent, or any combination thereof.
 16. Themethod of claim 1, wherein the (e) opacifying colorant is present in theaqueous foamed opacifying composition in an amount of at least 0.001weight % and up to and including 0.3 weight %, based on the total weightof the aqueous foamed opacifying composition.
 17. The method of claim 1,wherein the (e) opacifying colorant is a carbon black, a neutral blackpigment or a dye other than a carbon black, or a combination of two ormore of such materials.
 18. The method of claim 1, wherein the (e)opacifying colorant is located solely in the (a) porous particles. 19.The method of claim 1, wherein the aqueous foamed opacifying compositionfurther comprises an adhesive material.
 20. The method of claim 1,wherein the (b) binder material has a glass transition temperature(T_(g)) of less than 25° C.
 21. The method of claim 1, wherein the atleast one foaming surfactant and the at least one foam stabilizer areindependently one of the following compounds, or a mixture thereof:ammonium stearate, ammonium palmitate, sodium lauryl sulfate, ammoniumlauryl sulfate, ammonium or sodium alkyl sulfosuccinate, disodiumstearyl sulfosuccinate, diammonium n-octadecyl sulfosuccinamate,ethoxylated alcohols, a fatty acid soap, and a fatty acid condensationproduct with an alkylene oxide.